1220261 玖、發明說明： 【發明所屬之技術領域】 本發明關於一種在電解電容器中使用的電解液。 【先前技術】 近年來，出於電解電容器的低阻抗化之目的，迫切要 求一種高導電率的電解液。對此要求，原來提出有以芳族 羧酸的4級鏡鹽爲溶質之電解液（例如參照專利文獻1 )、 以順丁烯二酸的4級銨鹽、檸康酸的4級銨鹽爲溶質之電 解液（例如參照專利文獻2)的方案。 〔專利文獻1〕 日本專利公開1991 一 8092號公報（第1頁） 〔專利文獻2〕 日本專利公開1991 — 6646號公報（第1頁） 但是，這些電解液的導電率常常不充分。本發明之目 的就是提供一種高導電率的電解電容器用電解液。 【發明內容】 本發明者們爲了解決上述課題而進行了銳意的硏究， 結果發現該導電率不充分的原因是由於在電解液中含有不 純物，g卩（1)來自溶劑的不純物之溶劑的加水分解物質、（2) 來自電解質的陽離子成分的不純物之第3級胺及第3級銨 鹽、（3)來自電解質的陰離子成分的不純物之酯中的任一 項，而藉由降低其含量可提高導電率。 於是，第一，本發明之電解電容器用電解液，其特徵 是：一種在由r 一丁內酯、3 -甲基一 2—噁唑烷及2—吡 11469pif.doc/008 5 1220261 咯烷所組成的群中選擇的至少1種有機溶劑（B)中，使 由第4級銨陽離子（al)和羧酸陰離子（a2)所構成的電 解質鹽（A)溶解之電解液，其中下述一般式（1)、（ 2) 及（3)所示之有機溶劑的加水分解物（C)的基於電解液 的重量之合計重量含有率爲2%以下； 第二，本發明之電解電容器用電解液，其特徵是：一 種在有機溶劑（E)中使由第4級銨陽離子（gl)和羧酸 陰離子（g2)所構成的電解質鹽（G)溶解之電解液，其 中與該第4級銨暘離子（gl)相當之第3級胺（jl)及第 3級銨鹽（j2)的基於電解液的重量之合計重量含有率爲 1%以下； 第三，本發明之電解電容器用電解液，其特徵是：一 種使由鄰苯二甲酸陰離子、順丁烯二酸陰離子及檸康酸陰 離子所組成的群中挑選的至少1種羧酸陰離子（m2)和第 4級銨陽離子（ml)組成之電解質鹽（M)在有機溶劑（L) 中溶解之電解液，其中下述一般式（4)、（5)及（6)所 示之酯（N)的基於電解液的重量之合計重量含有率爲2% 以下。 ?1220261 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to an electrolytic solution used in an electrolytic capacitor. [Prior Art] In recent years, for the purpose of reducing the impedance of electrolytic capacitors, an electrolytic solution with high conductivity has been urgently required. In response to this request, electrolyte solutions using a fourth-order mirror salt of an aromatic carboxylic acid as a solute (for example, refer to Patent Document 1), a fourth-order ammonium salt of maleic acid, and a fourth-order ammonium salt of citraconic acid have been proposed. A solution that is a solute electrolyte (see, for example, Patent Document 2). [Patent Document 1] Japanese Patent Publication No. 1991-8092 (Page 1) [Patent Document 2] Japanese Patent Publication No. 1991-6646 (Page 1) However, the conductivity of these electrolytic solutions is often insufficient. The object of the present invention is to provide an electrolytic solution for electrolytic capacitors with high conductivity. [Summary of the Invention] The present inventors made earnest research in order to solve the above-mentioned problems, and found that the reason for the insufficient conductivity is that the electrolyte contains impurities, and g (1) of the solvent of the impurities from the solvent Either a hydrolysable substance, (2) a tertiary amine and a tertiary ammonium salt of an impure substance derived from a cationic component of an electrolyte, or (3) an ester of an impure substance derived from an anionic component of an electrolyte, and its content can be reduced Can improve conductivity. Therefore, first, the electrolytic solution for electrolytic capacitors according to the present invention is characterized in that it is characterized by r-butyrolactone, 3-methyl-2oxazolidine and 2-pyridine 11469pif.doc / 008 5 1220261 pyrrolidine. An electrolytic solution in which an electrolyte salt (A) composed of a fourth-order ammonium cation (al) and a carboxylic acid anion (a2) is dissolved in at least one organic solvent (B) selected from the group consisting of the following: The total weight content of the hydrolyzed product (C) of the organic solvent represented by the general formulae (1), (2), and (3) based on the weight of the electrolytic solution is 2% or less; Second, for the electrolytic capacitor of the present invention The electrolytic solution is characterized in that it is an electrolytic solution in which an electrolyte salt (G) composed of a fourth-order ammonium cation (gl) and a carboxylic acid anion (g2) is dissolved in an organic solvent (E), and the fourth The total weight content of the third ammonium sulfonium ion (gl) equivalent to the third amine (jl) and the third ammonium salt (j2) based on the weight of the electrolyte is 1% or less; third, for the electrolytic capacitor of the present invention Electrolyte, which is characterized by: an phthalate anion, maleic acid anion and citraconic anion An electrolyte solution in which an electrolyte salt (M) composed of at least one carboxylic acid anion (m2) and a fourth ammonium cation (ml) selected from the group consisting of organic molecules is dissolved in an organic solvent (L), wherein the following general formula The total weight content of the ester (N) shown in (4), (5), and (6) based on the weight of the electrolytic solution is 2% or less. ?
HO一CH2一CH2一CH2一C一OHHO-CH2-CH2-CH2-C-OH
HO一CH2一CH2—N—C—Ο 11469pif.doc/008 6HO-CH2-CH2—N—C—〇 11469pif.doc / 008 6
12202611220261
\^OCH 〇 (6) 【實施方式】 首先關於第1發明進行說明。 11469pif.doc/008 7 1220261 有關本發明之基於電解液重量之來自電解液的溶劑的 不純物之溶劑的加水分解物質（c)的合計含有量，通常 爲2重量％以下。在含有超過2重量％之該加水分解物質 的場合，導電率低下。電解液中的該加水分解物質的含有 量較佳爲1%重量以下，更佳爲0·5重量％以下。 作爲（c)，可舉出在溶劑中使用r - 丁內酯之場合由 上述一般式（Ο所示的物質羥基異丁酸〔以下記作（cl) 〕、在溶劑中使用3 —甲基-2—噁唑烷之場合由上述一般 式（2)所示的物質N—羥乙基一 N—甲胺基甲酸〔以下記 作（C2)〕及在溶劑中使用2-吡咯烷之場合由上述一般 式（3)所示的物質4一氨基丁酸〔以下記作（C3)〕。 本發明的電解液中所使用的溶劑（b)爲從由r - 丁 內酯、3-甲基一 2—噁唑烷及2—吡咯烷所組成的群中選 擇的至少1種，使用這些溶劑的電解液由於導電率高，可 抑制藉由溶劑的蒸發揮散而引起之電解液的乾膨脹（dry up)，且使用溫度範圍廣，所以被樂於使用。這些溶劑具 有各個酯鍵、尿烷鍵及醯胺鍵，所以在有水分存在的情況 下受到熱滯後之場合，被加水分解而生成上述所示之加水 分解物（C)。因此在以這些溶劑爲主成分而溶解溶質之電 解液中也會含有（C)。 本發明所規定之加水分解物（C)的含量可藉由例如 核磁共振吸收分析（1H - NMR)而定量。將1Η等具有磁 矩之原子核放入磁場中，當給予適當頻率的電磁場時產生 核磁共振，並吸收其電磁能量。可從被觀測之核磁共振吸 11469pif.doc/008 8 1220261 收的化學位移的位置、共振吸收的強度得到構造及定量的 見解。 加水分解物（c)內，由上述一般式（！）所示的， 在將電解液由重DMSO ( Dimethyl sulfoxide，二甲基亞颯） 進行稀釋並使用核磁共振吸收分析裝置在300MHz下實施 iH-NMR分析時，在〜3.5ppm〜的位置表現出2質子的 特徵峰値。由上述一般式（2)所示的，在同樣地實施ιΗ 一 NMR分析時，在〜3.8ppm〜的位置表現出2質子的特 徵峰値。由上述一般式（3 )所示的，在同樣地實施ιΗ一 NMR分析時，在〜2.7ppm〜的位置表現出2質子的特徵 峰値。藉由在電解液中添加已知量的標準物質，並將標準 物質的屮一 NMR峰値積分比和上述一般式（:042)43) 的1H—NMR積分比進行比較，可定量上述一般式（1)、 (2)、（ 3)的含有量。作爲標準物質可舉出氯仿、苯等， 以氯仿爲佳。 作爲將電解液中的（C)的含有量降低至2重量％以 下之方法，可舉出例如（1)藉由矽膠、活性炭、活性氧化鋁、 特殊的分子舖等而吸附處理（C)之方法、（2)在加熱電解 液的情況下，藉由進行減壓脫水而使成爲加水分解的要因 之水分在0.2重量％以下的方法、（3)調整電解液的酸/鹽 基平衡的方法。由於（C)特別是在鹽基性區域其生成被 促進，所以可藉由使形成電解質鹽（A)之第4級銨陽離 子（al )和羧酸陰離子（bl )的莫耳比率爲1 : 1〜1 : 1.05， 較佳爲1 ; 1〜1 : 1.02，將電解液從中性變爲弱酸性而抑 11469pif.doc/008 9 1220261 制其生成。在（1)的方法中，藉由吸附處理可使加水分解物 (C)降低至何種水平，取決於所用的吸附劑的種類及處 理條件。在(2)的方法中，爲了抑制其他的不純物的副產物， 溫度、減壓度等設定條件變得重要。（3)的方法中由於沒有 其他的不純物的副產物及混入的可能性所以較佳。（1)、 (2)、（3)的方法既可分別單獨進行，也可組合進行。 作爲本發明所用之第4級銨陽離子（al )，可舉出例 如下述之種類。 (1) 脂肪族第4級錢 四甲銨、乙基三甲基銨、甲基三乙基銨、四乙銨、二 乙基二甲基銨、四丙基銨、四丁基銨等 (2) 脂環族第4級銨 N，N—二甲基吡咯烷鑰、N，N—二乙基吡咯烷鏺、 N—甲基一 N—乙基吡咯烷鑰、N，N—二甲基呱啶鑰、N、 N-二乙基呱啶鑰等N—甲基吡啶鑰、N—乙基吡啶鑰等 (3) 芳族第4級銨 N—甲基吡啶鑰、N—乙基吡啶鑰等 作爲在本發明所用的羧酸陰離子（a2)上付加質子之羧酸 (a2’ ），可舉出例如下述之種類。 一元羧酸{ C1〜30的脂肪族一元羧酸〔飽和一元羧 酸（甲酸、乙酸、丙酸、丁酸、異丁酸、戊酸、己酸、庚 酸、辛酸、壬酸、十二烷酸、十四烷酸、十八烷酸、二十 二（碳）烷酸等）及不飽和一元羧酸（丙烯酸、甲基丙烯 酸、油酸等）〕及芳族一元羧酸〔苯甲酸、肉桂酸、萘甲 11469pif.doc/008 10 1220261 酸等〕}及聚羧酸（2〜4價的聚羧酸）{脂肪族聚羧酸〔飽 和聚羧酸（乙二酸、丙二酸、丁二酸、戊二酸、己二酸、 庚二酸、辛二酸、壬二酸、癸二酸等）；不飽和聚羧酸（順 丁烯二酸、檸康酸、反丁烯二酸、衣康酸等）〕；芳族聚羧 酸〔鄰苯二甲酸、間苯二甲酸、對苯二甲酸、偏苯三酸、 均苯四甲酸等〕；脂肪族羥酸〔羥基乙酸、乳酸、酒石酸 等〕；芳族羥酸〔水楊酸、扁桃酸等〕；含硫聚羧酸〔硫撐 丙酸〕及其它聚羧酸〔環丁烯一 1，2-二羧酸、環戊烯一 1，2-二羧酸、呋喃一2, 3-二羧酸、二環〔2, 2，1〕 庚院一 2 —稀—2，3 — —^竣酸、一環〔2，2 ’ 1〕七—2 — 烯—2, 3—二羧酸〕、二環〔2, 2, 1}七—2、5 —二烯— 2，3—二羧酸等} 這些裏面較佳的是導電率高、溶劑溶解性優的順丁烯 二酸和檸康酸，還有導電率高、熱穩定的芳族單羧酸、芳 族聚羧酸、芳族羥酸等。 作爲本發明的電解質鹽（A)，可舉出例如下述之種類。 鄰苯二甲酸單四甲銨、順丁烯二酸單四甲銨、檸康酸 單四甲銨、鄰苯二甲酸單乙基三甲基銨、順丁烯二酸單乙 基三甲基銨、檸康酸單乙基三甲基銨、鄰苯二甲酸單N， N—二甲基吡咯烷鎗、順丁烯二酸單N，N—二甲基吡略烷 鑰、檸康酸單N，N—二甲基吡咯烷鑰、鄰苯二甲酸單N， N-二乙基吡略烷鑰、順丁烯二酸單N，N-二乙基吡咯烷 鑰、檸康酸單N，N-二乙基吡咯烷鑰、鄰苯二甲酸單N -甲基吡啶鐺、順丁烯二酸單N-甲基吡啶鑰、檸康酸單 11469pif.doc/008 11 1220261 N—甲基吡啶鑰等。 本發明的電解液中之電解質鹽（A )的含量，從電氣 導電率的觀點來看，基於電解液的重量，較佳爲5%重量 以上，更佳爲10重量％以上，從對電解液溶劑之溶解度的 觀點來看，較佳爲70重量％以下，更佳爲40重量％以下。 在本發明的電解液中，根據需要，作爲副溶劑（B’ ） 可添加例如從以下的群中選擇的1種以上之溶劑。副溶劑 (B’ ）的添加量爲對電解液合計重量的〇重量％以上50 重量％以下。 (1)乙醇類 1價乙醇：碳數1〜6的1價乙醇（甲基乙醇、乙基乙 醇、丙基乙醇、丁基乙醇、雙丙酮乙醇、糠基乙醇等）、 碳數7以上的1價乙醇（苄基乙醇、辛醇等）、 2價乙醇：碳數1〜6的2價乙醇（乙二醇、丙二醇、 雙乙二醇、己二醇等）、碳數7以上的2價乙醇（辛二醇 等）、 3價乙醇：碳數1〜6的3價乙醇（丙二醇等）、 從4價到6價或其以上的乙醇：碳數1〜6的從4價 到6價或其以上的乙醇（己糖醇）。 (2)醚類 單醚（乙二醇單甲基醚、乙二醇單乙基醚、二乙二醇 單甲基醚、二乙二醇單乙基醚、乙二醇單苯基醚、四氫呋 喃、3單甲基四氫呋喃等）、二醚（乙二醇二甲基醚、乙二 醇二乙基醚、二乙二醇二甲基醚、二乙二醇二乙基醚等） 11469pif.doc/008 1220261 等。 (3) 醯胺類 甲醯胺類（N —甲基甲醯胺、N，N—二甲基甲醯胺、 N —乙基甲醯胺、N，N—二乙基甲醯胺等）、乙醯胺類（N 一甲基乙醯胺、N，N—二甲基乙醯胺、N—乙基乙醯胺、 N，N-二乙基乙醯胺等）、丙醯胺類（N，N一二甲基丙醯 胺、六甲基磷醯胺等）、噁唑烷類（3，5 —二甲基一 2一噁 口坐院等）。 (4) 內酯類 α —乙醯一r — 丁內酯、A —丁內酯、T —戊內酯、 5 —戊內酯等。 (5) 腈類 乙腈、丙烯腈等。 (6) 碳酸酯 碳酸乙烯酯、碳酸丙烯酯等。 (7) 其他有機極性溶劑 N—甲基吡咯烷、二甲基亞颯、環丁颯、1，3—二甲基一2 一味D坐院等。 上述之中較佳的是環丁颯、乙二醇。 在本發明的電解液中可根據需要，添加電解液中通常 所用之種種添加劑（D )。作爲該添加劑（D )，可舉出例 如磷酸衍生物（例如磷酸、磷酸酯等）、硼酸衍生物（例 如硼酸、硼酸和多糖類〔甘露糖醇、山梨糖醇等〕的錯合 物、硼酸和多價乙醇〔乙二醇、丙三醇等〕的錯合物等）、 11469pif.doc/008 13 1220261 硝基化合物（例如〇-硝基苯甲酸、P-硝基苯甲酸、m-硝基苯甲酸、〇-硝基苯酚、P-硝基苯酚等）等。（D)的 合計添加量爲對電解液合計重量的10重量％以下爲佳。 接著，關於第2發明進行說明。 有關本發明之來自電解液的電解質陽離子成分的不純 物之第3級胺（jl)及第3級銨鹽（」2)的基於電解液的 重量之合計含有量，在1%重量以下。在含有超過1重量％ (jl)及（j2)的場合，導電率低下。（jl)及（j2)的含 有量較佳爲0.5重量％以下，更佳爲0.2重量％以下。 作爲（jl)及（j2)，可舉出例如以下之種類。 (1)脂肪族第3級胺及3級銨鹽 脂肪族第3級胺：三甲基胺、乙基二甲基胺、甲基二 乙基胺、三乙基胺、三一N-丙胺、三丁胺、二乙基—i 一 丙胺等。 脂肪族第3級銨鹽：鄰苯二甲酸單三甲基銨鹽、順丁 烯二酸單三甲基銨鹽、檸康酸單三甲基銨鹽、順丁烯二酸 單乙基二甲基銨鹽、鄰苯二甲酸單乙基二甲基銨鹽、檸康 酸單乙基二甲基銨鹽、檸康酸單甲基二乙基銨鹽、鄰苯二 甲酸單甲基二乙基銨鹽、順丁烯二酸單甲基二乙基銨鹽、 鄰苯二甲酸單三乙基銨鹽、順丁烯二酸單三乙基銨鹽、檸 康酸單三乙基銨鹽、鄰苯二甲酸單三-N-丙銨鹽、順丁 嫌一酸單二一N-丙錶鹽、棒康酸單二一N-丙鏡鹽、鄰 苯二甲酸單三丁銨鹽、順丁烯二酸單三丁銨鹽、檸康酸單 三丁銨鹽、鄰苯二甲酸單二乙基一 1-丙銨鹽、順丁烯二 11469pif.doc/008 14 1220261 酸單二乙基一 i一丙銨鹽、檸康酸單二乙基—i一丙銨鹽等。 (2) 脂環式第3級胺及第3級銨鹽 脂環式第3級胺：N—甲基吡咯烷、N-乙基吡咯烷、 N-甲基呱啶、N—乙基呱啶等。 脂環式第3級銨鹽：鄰苯二甲酸單N-甲基吡咯烷鑰、 順丁烯二酸單N-甲基吡咯烷鐺、檸康酸單N-甲基吡咯 烷鑰、鄰苯二甲酸單N—乙基吡咯烷鑰、順丁烯二酸單N -乙基吡咯烷鐵、檸康酸單N-乙基吡咯烷鑷、鄰苯二甲 酸單N-甲基呱啶鑰、順丁烯二酸單N-甲基呱啶鑷、檸 康酸單N—甲基呱啶鑰、鄰苯二甲酸單N—乙基呱啶鑰、 順丁烯二酸單N-乙基呱啶鑰、檸康酸單N-乙基呱啶鑰 等。 (3) 芳族第3級胺及3級銨鹽 芳族第3級胺：吡啶等。 芳族第3級銨鹽：鄰苯二甲酸單吡啶鑷、順丁烯二酸 單吡啶鑰、檸康酸單吡啶鑰等。 本發明所規定之（jl)及（j2)的合計含有量，可藉 由例如液體色譜儀而定量。預先藉由已知濃度的（jl)及 (j2)的移動相溶液而進行液體色譜儀測定並製作校正曲 線後，由內部標準法依據定法進行定量。 作爲本發明的電解質鹽（G)之第4級銨鹽的代表性 製造方法，在有機溶劑（jl)中使碳酸二酯反應而4級化 之後，使酸反應，稍後進行脫碳酸、脫溶劑之方法等爲人 所知。當（jl)的4級化不充分時，在電解液中會混入（jl) 11469pif.doc/008 15 1220261 及（j2 )。 爲了降低電解液中的（jl )及（j2)，可舉出例如（1) 在藉由碳酸二酯的第3級胺的4級化反應之際極力提高其 轉化率的方法、（2)藉由將第4級銨鹽在減壓下進行加熱而 留舉殘留之第3級胺的方法、（3)藉由將第4級鉸鹽再結晶 而除去第3級銨鹽的方法等。在（1)的方法中，爲了極力完 全地進行轉化，原料莫耳比、溶劑、溫度、壓力、時間等 的反應條件的設定變得重要。而且，轉化的進行可藉由利 用液體色譜儀進行反應跟蹤而確認。在（2)的方法中，爲了 抑制其他不純物的副產物，所以溫度、減壓度等設定條件 變得重要。在的方法中進行再結晶之際，再結晶所使用 的溶劑的種類、量、晶析溫度、次數等條件變得重要。（1)、 (2)、（3)的方法既可以單獨進行，也可以組合進行。 作爲本發明的電解質鹽（G)，可舉出例如上述所舉之 電解質鹽（A)。 作爲本發明所用之有機溶劑（E)，可舉出例如上述所 舉之有機溶劑（B)。而且，有機溶劑（E)根據需要，可 對電解液合計重量添加〇重量％以上50重量％以下之上述 所舉的副溶劑（B’ ）。 作爲有機溶劑（E)，較佳爲丫一丁內酯、3 —甲基一 2 一噁唑烷、2—吡略烷。 作爲相當於本發明的第3級胺及第3級銨鹽之第4級 銨鹽（gl )，可舉出例如上述作爲（al )所例示之種類。 作爲本發明的羧酸陰離子（g2 )，可舉出例如上述作 11469pif.doc/008 爲（a2)所例示之種類。 本發明的電解液之電解質鹽（G)的含量，從電氣導 電率的觀點出發，較佳爲基於電解液之重量的5重量％以 上，更佳爲10重量％以上，從對電解液溶劑的溶解度的觀 點出發，較佳爲70重量％以下，更佳爲40重量％以下。 在本發明的電解液中，根據需要可添加電解液所通常 使用之種種的添加劑（K)。作爲該添加劑（K)，可舉出 上述作爲（D)所例示之種類。（K)的合計含有量在對電 解液合計重量的10重量％以下爲佳。 接著關於第3發明進行說明。 有關本發明之來自電解液的電解質陰離子成分的不純 物之酯（N)，即上述一般式（4)所示之酯、鄰苯二甲酸 單甲基酯（N1)，上述一般式（5)所示之酯、順丁烯二酸 單甲基酯（N2)，及上述一般式（6)所示之酯、檸康酸單 甲基酯（N3)的基於電解液的重量之合計含有量，在2% 重量以下。在含有量超過2重量％的場合，導電率低下。 含有量較佳爲1重量％以下，更佳爲0.5重量％以下。 作爲本發明的電解質鹽（M)之第4級銨鹽的代表性 製造方法，有在乙醇溶劑中，使在第3級胺中使碳酸二酯 反應而4級化之物質，在將無水鄰苯二甲酸及/或無水順 丁烯二酸及/或無水檸康酸以水進行加水分解之物質中進 行反應，稍後進行脫水、脫碳酸、脫溶劑之方法。 在無水鄰苯二甲酸及/或無水順丁烯二酸及/或無水 檸康酸的加水分解不充分之場合，它們在電解液中會有殘 11469pif.doc/008 17 留。殘留之無水鄰苯二甲酸及/或無水順丁烯二酸及/或 無水檸康酸與反應溶劑之乙醇等進行反應，生成上述一般 式（4 )、（ 5 )及（6 )的酯（N )。 本發明所規定之酯的含量可藉由例如核磁共振吸收分 析（NMR)而定量。 (N)的任一個都可在以重DMS〇稀釋電解液，使用 核磁共振吸收分析裝置以3〇〇MHz實施lH__NMR分析時， 在〜3.8PPm〜的位置表現出3質子的特徵峰値。藉由在電 解液中添加已知量的標準物質並將標準物質的lH 一 nmr 峰値積分比和上述（N)的1H-NMR峰値積分比進行比 較，可定量上述（N)的含有量。作爲標準物質，可舉出 氯仿、苯等，較佳爲氯仿。 —爲了降低電賴中的（N)，可舉出例_)在無水鄰 本一=酸、無水順丁燦二酸及無水檸^^酸的加水分解時極 力提筒其__方法、⑺藉喃第4 __結晶而除 去殘留之不純物的方法等。在（1)的方法中使轉化率提高到 何種水平，水和酸無水物的莫耳比、溫度、時間等的反應 條件的選疋是重要的。在(2)的方法中進行再結晶時，再結 曰曰所使用的i谷h!I的種類、屋：、晶析溫度、次數等條件是重 要的。（1)、（2)的方法既可單獨進行，也可組合進行。 作爲本發明所使用之第4級銨陽離子（ml)，可舉出 上述作爲（al)所例示之種類。 作爲本發明的電解質鹽（M)，可舉出例如上述所舉 之電解質鹽（A)。 11469pif.doc/008 18 1220261 作爲本發明所使用之有機溶劑（L)，可舉出例如上述 所舉之有機溶劑（B)。而且，有機溶劑（L)可根據需要， 添加對電解液合計重量的〇重量％以上5〇重量％以下之上 述所舉的副溶劑（B’ ）。 作爲有機溶劑（L )，較佳爲Y -丁內酯、3 一甲基〜2 一噁唑烷、2 -吡咯烷。 本發明的電解液之電解質鹽（Μ)的含量’從電氣導 電率的觀點出發，較佳爲基於電解液之重量的5重量％以 上，更佳爲10重量％以上，從對電解液溶劑的溶解度的觀 點出發，較佳爲70重量％以下，更佳爲40重量％以下。 在本發明的電解液中，根據需要可添加電解液所通常 使用之種種的添加劑（Ρ)。作爲該添加劑（Ρ)，可舉出上 述作爲（D )所例75之種類。（Ρ )的合計含有量在對電解 液合計重量的10重量％以下爲佳。 本發明第1、第2以及第3發明的電解液可用於電解 電容器中。 接著關於本發明之具體的實施例進行說明，但是本發 明並不限定於此。 <電解液的調製> 實施例1 在1L咼壓签中裝入甲醇67.3g和二甲基碳酸醋66.2g (0.74莫耳）’在密閉下升溫至12〇它。接著在加壓下，用 1〇小時吹入三甲基胺41.4g (0.7莫耳）進行4級化反應。 反應液的4級化轉化率爲92.6%。之後，將溫度提高到U5 11469pif.doc/008 19 1220261 ，一面由液體色譜儀跟蹤反應一面再繼續反應使4級化 轉化率達到99.9%以上，並得到四甲基銨一甲基碳酸鹽的 甲醇溶液174.9g。 在1L4 口燒瓶中裝入無水鄰苯二甲酸i〇8.8g ( 〇·74莫 耳）和大量過剩的離子交換水189.0g ( 10.5莫耳），在95 °C下進行2小時的加水分解反應。1H-NMR分析的結果， 無水鄰苯二甲酸的加水分解率爲99.9%。接著，用4小時 滴下上述之四甲基銨-甲基碳酸鹽174.9g以使酸/鹽基莫 耳比成1·〇5。滴下結束後，以120°C、常壓隨後減壓而進 行脫碳酸、脫溶劑、脫水’得到四甲基銨-鄰苯二甲酸鹽 206g。由市場上出售的Y—丁內酯將其稀釋使鹽濃度變爲 25重量％，並考慮在電容器內從電解紙混入的水分，將水 分調整至5·5wt%，完成電解液。 ^H — NMR分析及液體色譜儀分析的結果，（C1)的含 有量爲O.Olwt%，（ C2 )的含有量爲Owt%，（ C3 )的含有 量爲Owt%，所以溶劑的加水分解物（C)的合計含有量爲 O.Olwt%。 而且，來自陽離子的不純物第3級胺（D)之三甲基 及第3級銨鹽（j2)之三甲基銨鹽的合計含有量爲〇.03wt%。 另外，（N1 )的含有量爲〇wt%’（ N2 )的含有量爲〇wt% ’ (N3)的含有量爲0wt% ’所以來自陰離子的不純物酯（N) 的合計含有量爲0wt% ° 實施例2 除了使二甲基碳酸酯66.2g (0.74莫耳）以二乙基碳 2 0 11469pif.doc/008 酸酯86.8g (0.74莫耳）取代、三甲基胺4l.4g (〇·7莫耳） 以N—甲基卩比略院69·4§ ( 0·7莫耳）取代、無水—本一甲 酸108.8g (0·74莫耳）以無水順丁烯二酸72；〇g (〇·74莫 耳）取代以外，與實施例1同樣地調製電解液。力外，在 1201：下之4級反應後的4級化轉化率爲9 1 _6 /°。 - NMR分析及液體色譜儀分析的結果，（C1)的含 有量爲O.Olwt%，（C2)的含有量爲〇wt%，（C3)的含有 量爲Owt%，所以（C)的合計含有量爲0.01wt%。而且，、 來自陽離子的不純物（·Π)及U2)的合計含有量爲 0.02wt%。另外，（N1 )的含有量爲〇wt%，（ N2)的含有 量爲〇wt%，（ N3 )的含有量爲〇wt%，所以（N)的合曰十 含有量爲Owt%。 實施例3 除了使無水鄰苯二甲酸l〇8.8g (〇·74莫耳）以無水棒 康酸82.3g (0.74莫耳）取代以外，與實施例1同樣地調 製電解液。另外，在120°C下之4級反應後的4級化轉化 率爲91.4%。 - NMR分析及液體色譜儀分析的結果’（C1)的含 有量爲O.Olwt%，（C2)的含有量爲〇Wt%’（C3)的含有 量爲Owt%，所以（C)的合計含有量爲0.01wt%。而且’ 來自陽離子的不純物（jl)及（j2)的合^計#有*胃胃 0.02wt%。另外，（N1)的含有量爲〇wt%，（N2)的含有 量爲Owt%，（ N3 )的含有量爲Owt%，所以（N)的合計 含有量爲〇wt%。 11469pif.doc/008 1220261 實施例4 除了使γ-丁內酯以3-甲基一 2-噁唑烷取代以外， 與實施例1同樣地調製電解液。另外，在120°C下之4級 反應後的4級轉化率爲91.4%。 iH- NMR分析及液體色譜儀分析的結果，（C1 )的含 有量爲Owt%，（ C2)的含有量爲O.Olwt%，（ C3)的含有 量爲Owt%，所以（C)的合計含有量爲O.Olwt%。而且， 來自陽離子的不純物（j 1 )及（j2 )的合計含有量爲 0.02wt%。另外，（N1)的含有量爲Owt%，（N2)的含有 量爲Owt%，（N3)的含有量爲Owt%，所以（N)的合計 含有量爲Owt%。 實施例5 除了使γ—丁內酯以2-吡咯烷取代以外，與實施例1 同樣地調製電解液。另外，在120°C下之4級反應後的4 級轉化率爲91.5%。 -NMR分析及液體色譜儀分析的結果，（C1 )的含 有量爲Owt%，（ C2)的含有量爲Owt%，（ C3 )的含有量 爲0.02wt%，所以（C)的合計含有量爲0.02wt%。而且， 來自陽離子的不純物（jl )及（j2 )的合計含有量爲 0.02wt%。另外，（N1 )的含有量爲Owt%，（ N2 )的含有 量爲Owt%，（ N3 )的含有量爲Owt%，所以（N )的合計 含有量爲Owt%。 比較例1 除了使無水鄰苯二甲酸的裝入量爲98.4g (0.67莫 11469pif.doc/008 2 2 1220261 耳）、酸/鹽基莫耳比爲0.96以外，與實施例1同樣地調 製電解液。 β - NMR分析及液體色譜儀分析的結果，（C1 )的含 有量爲3.1wt%，（ C2)的含有量爲Owt%，（ C3)的含有量 爲Owt%，所以（C )的合計含有量爲3.1wt%。而且，來 自陽離子的不純物（jl)及（j2)的合計含有量爲0.03wt%。 另外，（N1 )的含有量爲〇wt%，（ N2 )的含有量爲Owt%， (N3 )的含有量爲〇wt%，所以（N)的合計含有量爲Owt%。 比較例2 除了不實施在實施例1中的4級化反應時在135°C下 的再加熱反應，且使γ—丁內酯以2一吡咯烷取代以外’ 與實施例1同樣地調製電解液。 iH - NMR分析及液體色譜儀分析的結果，（C1 )的含 有量爲O.Olwt%，（ C2)的含有量爲〇wt%，（ C3)的含有 量爲Owt%，所以（C)的合計含有量爲〇.〇lwt%。而且， 來自陽離子的不純物（jl)及U2)的合計含有量爲。 另外，（N1 )的含有量爲〇wt%，（ N2 )的含有量爲Owt%， (N3 )的含有量爲Owt%，所以（N)的合計含有量爲〇wt%。 比較例3 除了使在實施例3的無水檸康酸的加水分解反應之 際，離子交換水的量爲18.9g ( 1·〇5莫耳）以外，與實施 例2同樣地調製電解液。 β - NMR分析及液體色譜儀分析的結果，（C1 )的含 有量爲〇.〇lwt%，（C2)的含有量爲〇wt%，（C3)的含有 11469pif.doc/008 23 1220261 量爲〇wt%，所以（C)的合計含有量爲O.Olwt%。而f ’、 來自陽離子的不純物（jl)及（j2)的合計含有*胃胃 0.02wt%。另外，（N1 )的含有量爲Owt%，（ N2)的含有 量爲0wt%，（N3)的含有量爲3.2wt%，所以（N)的合曰十 含有量爲3.2wt%。 比較例4 除了使實施例4之無水鄰苯二甲酸的裝入量爲98.4g (0.67莫耳）、酸/鹽基莫耳比爲0.96以外，與實施例4 同樣地調製電解液。 iH-NMR分析及液體色譜儀分析的結果，（C1)的含 有量爲Owt%，（ C2)的含有量爲2.9wt%，（ C3)的含有量 爲Owt%，所以（C)的合計含有量爲2.9wt%。而且，來 自陽離子的不純物（jl )及（j2 )的合計含有量爲〇.〇2wt%。 另外，（N1)的含有量爲Owt%，（N2)的含有量爲〇wt%， (N3)的含有量爲Owt%，所以（N)的合計含有量爲〇wt%。 比較例5 ° 除了使實施例5之無水鄰苯二甲酸的裝入量爲9 (0.67莫耳）、酸/鹽基莫耳比爲〇·96以外，與實施9^4g 同樣地調製電解液。 ά U 5 β- NMR分析及液體色譜儀分析的結果，（ 有量爲Owt%，（ C2 )的含有量爲〇wt〇/〇，（ C3 )的含玲 爲4.0wt%，所以（C)的合計含有量爲4 〇wtG/。。而且奧 自陽離子的不純物（j〗）及（j2)的合計含有量爲〇 j來 另外’（N1)的含有里爲〇wt%，（N2)的含有|佐、 里瑪〇wt%， 11469pif.doc/008 24 1220261 (N3)的含有量爲〇wt%，所以（N)的合計含有量爲〇wt%。 將實施例1〜5及比較例1〜5中所述之電解液中的不 純物的含有量彙集於表1中。lH—NMR分析及液體色譜 儀分析的測定條件如下。 < NMR 分析 > 裝置：核磁共振吸收分析裝置A— 300 (日本Bruker 公司製） 測定溶劑：重DMSO 頻率：300MHz <液體色譜儀分析> 裝置：高速液體色譜儀LC - 10A (島津製作所製） 柱體：Capcell PAK ( SHISEIDO 公司製） 移動相：含有磷酸l〇mM和高氯酸鈉i〇〇mM之離子 交換水。 流速：〇.8ml/min 樣品稀釋倍率：由移動相進行100倍稀_ 樣品注入量：20μ1 檢測器：UVIDEC— 100V 檢測波長：210nm 使用實施例1〜5及比較例1〜5的電解液，測定 導電率，在表1中表示其結果。 11469pif.doc/008 25 〔一撇〕 導電率 _ (mS/cm) 11.4 15.7 12.0 10.0 10.0 〇6 σν \〇 (N (Ν 〇 (N) (wt%) ο 〇 〇 〇 〇 〇 〇 Γν| 〇 〇 (Jl)及（J2) (wt% ) 0.03 0.02 i_ 0.02 0.02 0.02 ! 0.03 CX) ! 11 Μ 0.01 0.02 0.02 U (wt% ) 0.01 0.01 0.01 0.01 0.02 1 冷 0.01 0.01 On (N 〇 電解液 混合比 1 Γ in in in in in in in L 丨 CN (N (Ν <N (Ν (Ν (N <N <N (Ν ! 溶劑 γ—丁刚旨 γ—丁內酯 γ—丁刚旨 3 —甲基一2 — 噁唑烷 2 -吡咯烷 γ—丁內酯 2 -吡咯烷 γ—丁內醋 3 —甲基一2 — 噁唑烷 2 -吡咯烷 電解質 鄰苯二甲酸單四甲基銨 順丁烯二酸單Ν，Ν-二 乙基銨 檸康酸單四甲基銨 鄰苯二甲酸單四甲基銨 鄰苯二甲酸單四甲基銨 鄰苯二甲酸單四甲基銨 鄰苯二甲酸單四甲基銨 檸康酸單四甲基銨 鄰苯二甲酸單四甲基銨 鄰苯二甲酸單四甲基銨 、 1 / j 實施例1 實施例2 實施例3 實施例4 實施例5 比較例1 比較例2 : 比較例3 比較例4 j 1 比較例5 9CVJ·OO00POSU69寸一一 1220261 <導電率> 使用東亞電波(股)公司製導電率計CM- 40S，測定在30 °C的導電率。 由表1可知，本發明的實施例1〜5的電解液與比較例1 〜5的電解液相比，具有優良的導電率特性。 本發明的電解液由於不純物之溶劑的加水分解物·、第3 級胺及第3級銨鹽以及酯的含有量少，所以導電率優良。因 此藉由使用本發明的電解液可謀求電解電容器的高性能化。 11469pif.doc/008 27\ ^ OCH 〇 (6) [Embodiment] First, the first invention will be described. 11469pif.doc / 008 7 1220261 The total content of the hydrolysable substance (c) of the solvent-impurity-solvent-based solvent of the electrolyte based on the weight of the electrolyte of the present invention is usually 2% by weight or less. When the hydrolyzable substance is contained in an amount exceeding 2% by weight, the conductivity is low. The content of the hydrolyzable substance in the electrolytic solution is preferably 1% by weight or less, and more preferably 0.5% by weight or less. As (c), when r-butyrolactone is used in a solvent, hydroxyisobutyric acid [hereinafter referred to as (cl)], which is a substance represented by the general formula (0), and 3-methyl in a solvent can be mentioned. In the case of 2-oxazolidine, the substance represented by the general formula (2) above is N-hydroxyethyl-N-methylaminocarboxylic acid [hereinafter referred to as (C2)] and in the case of using 2-pyrrolidine in a solvent Substance 4-aminobutyric acid [hereinafter referred to as (C3)] represented by the above general formula (3). The solvent (b) used in the electrolytic solution of the present invention is derived from r-butyrolactone, 3-form At least one selected from the group consisting of 2-oxazolidine and 2-pyrrolidine. Electrolytes using these solvents have high electrical conductivity, and can suppress the dry expansion of the electrolyte caused by evaporation of the solvent. (Dry up), and a wide range of temperature, so they are happy to use. These solvents have various ester bonds, urethane bonds, and amido bonds, so in the presence of moisture in the presence of thermal hysteresis, they will be hydrolyzed to form The hydrolyzed product (C) shown above. Therefore, these solvents are used as the main component to dissolve the solute. (C) may also be contained in the electrolytic solution. The content of the hydrolysate (C) specified in the present invention can be quantified by, for example, nuclear magnetic resonance absorption analysis (1H-NMR). Nuclei having a magnetic moment such as 1Η are placed in a magnetic field. In the experiment, when an electromagnetic field with an appropriate frequency is given, nuclear magnetic resonance is generated and its electromagnetic energy is absorbed. The position of the chemical shift and the intensity of resonance absorption can be obtained from the observed nuclear magnetic resonance absorption 11469pif.doc / 008 8 1220261. Insights: In the hydrolysate (c), as shown in the above general formula (!), The electrolyte was diluted with heavy DMSO (Dimethyl sulfoxide, dimethyl sulfoxide) and the NMR absorption analysis device was used at 300 MHz. When iH-NMR analysis was performed, a characteristic peak of 2 protons was shown at a position of ~ 3.5 ppm ~. As shown in the above general formula (2), when NMR analysis was performed in the same manner, it was at ~ 3.8 ppm ~ The position shows a characteristic peak 2 of 2 protons. As shown in the general formula (3) above, when the Η-NMR analysis is performed in the same manner, the characteristic peak 2 of 2 protons appears at a position of ~ 2.7 ppm ~. electrolysis A known amount of standard substance is added to the solution, and the integral ratio of the first NMR peak of the standard substance and the 1H-NMR integral ratio of the general formula (: 042) 43) can be compared to quantify the general formula (1), (2) and (3). Examples of the standard substance include chloroform and benzene, and chloroform is preferred. Examples of the method for reducing the content of (C) in the electrolytic solution to 2% by weight or less include, for example, (1) the adsorption treatment of (C) by silica gel, activated carbon, activated alumina, special molecular coating, etc. Method, (2) a method of dehydrating under reduced pressure and dehydrating to reduce the water content to 0.2% by weight due to dehydration under heating, and (3) a method of adjusting the acid / base balance of the electrolyte . Since (C) is promoted especially in the base region, the molar ratio of the fourth-order ammonium cation (al) and carboxylic acid anion (bl) forming the electrolyte salt (A) can be 1: 1 ~ 1: 1.05, preferably 1; 1 ~ 1: 1.02, changes the electrolyte from neutral to weakly acidic and suppresses its production by 11469pif.doc / 008 9 1220261. In the method (1), the level to which the hydrolysate (C) can be reduced by the adsorption treatment depends on the type of the adsorbent used and the processing conditions. In the method (2), in order to suppress other by-products of impurities, setting conditions such as temperature and degree of decompression become important. The method (3) is preferable because there are no other by-products of impurities and the possibility of mixing. The methods (1), (2), and (3) may be performed individually or in combination. Examples of the fourth-order ammonium cation (al) used in the present invention include the following. (1) aliphatic 4th grade tetramethylammonium, ethyltrimethylammonium, methyltriethylammonium, tetraethylammonium, diethyldimethylammonium, tetrapropylammonium, tetrabutylammonium, etc. ( 2) Cycloaliphatic ammonium N, N-dimethylpyrrolidine, N, N-diethylpyrrolidine, N-methyl-N-ethylpyrrolidine, N, N-dimethyl N-methylpyridine, N, N-diethylpyridine, N-ethylpyridine, etc. (3) Aromatic 4th ammonium N-methylpyridine, N-ethyl As the carboxylic acid (a2 ') to which a proton is added to the carboxylic acid anion (a2) used in the present invention, pyridine key and the like include the following types. Monocarboxylic acids {C1 ~ 30 aliphatic monocarboxylic acids [saturated monocarboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, dodecane Acid, myristic acid, octadecanoic acid, docosalic acid, etc.) and unsaturated monocarboxylic acids (acrylic acid, methacrylic acid, oleic acid, etc.)] and aromatic monocarboxylic acids [benzoic acid, Cinnamic acid, naphthyl methyl 11469pif.doc / 008 10 1220261 acids, etc.]} and polycarboxylic acids (2- to 4-valent polycarboxylic acids) {aliphatic polycarboxylic acids [saturated polycarboxylic acids (oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc .; unsaturated polycarboxylic acids (maleic acid, citraconic acid, fumaric acid, etc.) Acid, itaconic acid, etc.)]; aromatic polycarboxylic acids [phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.]; aliphatic hydroxy acids [glycolic acid, Lactic acid, tartaric acid, etc.]; aromatic hydroxy acids [salicylic acid, mandelic acid, etc.]; sulfur-containing polycarboxylic acids [thiopropionic acid] and other polycarboxylic acids [cyclobutene-1,2-dicarboxylic acid, cyclic Ene-1,2-dicarboxylic acid, furan-2,3-dicarboxylic acid, bicyclic [2, 2,1] Gengyuan-1 2-dilute -2,3--^ complete acid, one ring [2,2 '1] hepta-2—ene-2, 3-dicarboxylic acid], bicyclo [2, 2, 1} hepta-2, 5-diene-2, 3-dicarboxylic acid, etc.} Among these, They are maleic acid and citraconic acid with high conductivity and excellent solvent solubility, as well as aromatic monocarboxylic acids, aromatic polycarboxylic acids, and aromatic hydroxy acids with high conductivity and thermal stability. Examples of the electrolyte salt (A) of the present invention include the following. Monotetramethylammonium phthalate, monotetramethylammonium maleate, monotetramethylammonium citrate, monoethyltrimethylammonium phthalate, monoethyltrimethylmaleate Ammonium, monoethyltrimethylammonium citraconic acid, mono N, N-dimethylpyrrolidine phthalate, maleic acid N, N-dimethylpyrrolidine, citraconic acid Mono N, N-dimethylpyrrolidine, phthalic acid mono N, N-diethylpyrrolidine, maleic acid mono N, N-diethylpyrrolidine, citraconic acid mono N, N-diethylpyrrolidine, phthalic acid mono-N-methylpyridine, maleic acid mono-N-methylpyridine, citraconic acid mono 11469pif.doc / 008 11 1220261 N-formyl Pyridyl key and so on. From the viewpoint of electrical conductivity, the content of the electrolyte salt (A) in the electrolytic solution of the present invention is preferably 5% by weight or more, more preferably 10% by weight or more based on the weight of the electrolytic solution. From the viewpoint of the solubility of the solvent, it is preferably 70% by weight or less, and more preferably 40% by weight or less. In the electrolytic solution of the present invention, as the auxiliary solvent (B '), one or more solvents selected from the following groups can be added, for example. The amount of the sub-solvent (B ') added is 0% by weight or more and 50% by weight or less based on the total weight of the electrolytic solution. (1) Ethanol monovalent ethanol: Monovalent ethanol with 1 to 6 carbon atoms (methyl ethanol, ethyl ethanol, propyl ethanol, butyl ethanol, diacetone ethanol, furfuryl alcohol, etc.) Monovalent ethanol (benzylethanol, octanol, etc.), divalent ethanol: divalent ethanol (ethylene glycol, propylene glycol, diethylene glycol, hexanediol, etc.) having a carbon number of 1 to 6, and 2 having a carbon number of 7 or more Valence ethanol (octanediol, etc.), Trivalent ethanol: Trivalent ethanol (propylene glycol, etc.) having 1 to 6 carbon atoms, Ethanol from 4 to 6 valences or more: From 4 to 6 carbon atoms Valence or higher ethanol (hexitol). (2) Ether monoethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monophenyl ether, Tetrahydrofuran, 3 monomethyltetrahydrofuran, etc.), diethers (ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc.) 11469pif. doc / 008 1220261, etc. (3) Methylamines Methylamines (N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, etc.) Acetamides (N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, etc.), propylamines (N, N-dimethylpropanamide, hexamethylphosphamide, etc.), oxazolidines (3,5-dimethyl-2, 2-oxaloxacin, etc.). (4) Lactones α-Acetyl-r-butyrolactone, A-butyrolactone, T-valerolactone, 5-valerolactone, etc. (5) Nitriles Acetonitrile, acrylonitrile, etc. (6) Carbonate Ethylene carbonate, propylene carbonate, etc. (7) Other organic polar solvents: N-methylpyrrolidine, dimethyl sulfene, cyclamidine, 1,3-dimethyl-12, etc. Among the above, cyclamidine and ethylene glycol are preferred. In the electrolytic solution of the present invention, various additives (D) generally used in the electrolytic solution can be added as necessary. Examples of the additive (D) include phosphoric acid derivatives (such as phosphoric acid and phosphate esters), boric acid derivatives (such as complexes of boric acid, boric acid, and polysaccharides [mannitol, sorbitol, etc.], and boric acid). And multivalent ethanol [ethylene glycol, glycerol, etc.], 11469pif.doc / 008 13 1220261 nitro compounds (such as 0-nitrobenzoic acid, P-nitrobenzoic acid, m-nitro Benzoic acid, 0-nitrophenol, P-nitrophenol, etc.). The total amount of (D) added is preferably 10% by weight or less based on the total weight of the electrolytic solution. Next, a second invention will be described. The total content of the tertiary amine (jl) and the tertiary ammonium salt ("2) related to the impurities of the electrolyte cation component derived from the electrolytic solution of the present invention is 1% by weight or less based on the weight of the electrolytic solution. When it contains more than 1% by weight (jl) and (j2), the conductivity is low. The content of (jl) and (j2) is preferably 0.5% by weight or less, and more preferably 0.2% by weight or less. Examples of (jl) and (j2) include the following. (1) aliphatic tertiary amines and tertiary ammonium salts, aliphatic tertiary amines: trimethylamine, ethyldimethylamine, methyldiethylamine, triethylamine, tri-N-propylamine , Tributylamine, diethyl-i-propylamine, etc. Aliphatic grade 3 ammonium salts: monotrimethylammonium phthalate, monotrimethylammonium maleate, monotrimethylammonium citrate, monoethyldimaleate Methylammonium salt, monoethyldimethylammonium phthalate, monoethyldimethylammonium citrate, monomethyldiethylammonium citrate, monomethyldiphthalate Ethyl ammonium salt, maleic acid monomethyl diethylammonium salt, phthalic acid monotriethylammonium salt, maleic acid monotriethylammonium salt, citraconic acid monotriethylammonium salt Salt, monotri-N-propylammonium phthalate, mono-N-propanedioic acid, mono-n-propanedioic acid, mono-N-propionate of glutamic acid, monotributylammonium phthalate , Maleic acid monotributylammonium salt, citraconic acid monotributylammonium salt, phthalic acid monodiethyl-1 -propane ammonium salt, maleic acid 11469pif.doc / 008 14 1220261 Ethyl-i-propylammonium salt, citraconic acid monodiethyl-i-propylammonium salt, etc. (2) Alicyclic tertiary amines and tertiary ammonium salts alicyclic tertiary amines: N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpyridine, N-ethylpyrene Pyridine and so on. Alicyclic tertiary ammonium salt: phthalic acid mono-N-methylpyrrolidine, maleic acid mono-N-methylpyrrolidine, citraconic acid mono-N-methylpyrrolidine, o-benzene Mono-N-ethylpyrrolidine dicarboxylic acid, mono-N-ethylpyrrolidine iron maleate, mono-N-ethylpyrrolidine tweezerate, mono-N-methylpyridine phthalate, Maleic acid mono-N-methylpyridine tweezers, citraconic acid mono-N-methylpyridine, maleic acid mono-N-ethylpyridine, maleic acid mono-N-ethylpyridine Pyrimidine, citraconic acid mono-N-ethylpyridine, and the like. (3) Aromatic tertiary amines and tertiary ammonium salts Aromatic tertiary amines: pyridine and the like. Aromatic tertiary ammonium salts: phthalic acid monopyridine tweezers, maleic acid monopyridine, citraconic acid monopyridine, etc. The total content of (jl) and (j2) specified in the present invention can be quantified by, for example, a liquid chromatograph. The liquid chromatograph was measured in advance with a mobile phase solution of known concentrations (jl) and (j2), and a calibration curve was prepared, and then quantified by the internal standard method according to the determination method. As a typical production method of the fourth-stage ammonium salt of the electrolyte salt (G) of the present invention, after the carbonic acid diester is reacted in the organic solvent (jl) to undergo fourth-stage conversion, the acid is reacted, and decarbonation and decarbonation are performed later. The solvent method and the like are known. When the (4) level of (jl) is insufficient, (jl) 11469pif.doc / 008 15 1220261 and (j2) are mixed in the electrolyte. In order to reduce (jl) and (j2) in the electrolytic solution, for example, (1) a method of maximizing the conversion rate of a tertiary reaction of a tertiary amine of a carbonic acid diester, (2) A method of retaining the remaining third-order amine by heating the fourth-order ammonium salt under reduced pressure, (3) a method of removing the third-order ammonium salt by recrystallizing the fourth-stage hinge salt, and the like. In the method (1), in order to perform the conversion as completely as possible, it is important to set the reaction conditions such as the molar ratio of the raw materials, solvent, temperature, pressure, and time. Furthermore, the progress of the conversion can be confirmed by performing reaction tracking using a liquid chromatograph. In the method (2), in order to suppress by-products of other impurities, setting conditions such as temperature and degree of decompression become important. When recrystallization is performed in the method, conditions such as the type, amount, crystallization temperature, and number of solvents used for recrystallization become important. The methods (1), (2), and (3) may be performed individually or in combination. Examples of the electrolyte salt (G) of the present invention include the above-mentioned electrolyte salt (A). Examples of the organic solvent (E) used in the present invention include the organic solvents (B) mentioned above. The organic solvent (E) may be added to the total weight of the electrolytic solution of 0% by weight or more and 50% by weight or less of the above-mentioned auxiliary solvents (B ') as necessary. The organic solvent (E) is preferably a-butyrolactone, 3-methyl- 2 -oxazolidine, and 2-pyrrolidine. Examples of the fourth-order ammonium salt (gl) corresponding to the third-order amine and the third-order ammonium salt of the present invention include the species exemplified above as (al). Examples of the carboxylic acid anion (g2) of the present invention include the species exemplified in the above-mentioned operation 11469pif.doc / 008 as (a2). The content of the electrolyte salt (G) of the electrolytic solution of the present invention is preferably 5% by weight or more, more preferably 10% by weight or more based on the weight of the electrolytic solution. From the viewpoint of solubility, it is preferably 70% by weight or less, and more preferably 40% by weight or less. In the electrolytic solution of the present invention, various additives (K) generally used in the electrolytic solution may be added as necessary. Examples of the additive (K) include those exemplified as the above (D). The total content of (K) is preferably 10% by weight or less based on the total weight of the electrolytic solution. Next, a third invention will be described. The ester (N) of the impurity of the electrolyte anion component derived from the electrolytic solution of the present invention is the ester represented by the general formula (4) and the monomethyl phthalate (N1). The total content of the ester, maleic acid monomethyl ester (N2), and the ester represented by the general formula (6) and citraconic acid monomethyl ester (N3) based on the weight of the electrolytic solution, Below 2% by weight. When the content exceeds 2% by weight, the conductivity is low. The content is preferably 1% by weight or less, and more preferably 0.5% by weight or less. As a representative method for producing the fourth-order ammonium salt of the electrolyte salt (M) of the present invention, there is a substance which is converted into a fourth-order by reacting a carbonic acid diester with a third-order amine in an ethanol solvent, and Phthalic acid and / or anhydrous maleic acid and / or anhydrous citraconic acid are reacted in a substance hydrolyzed with water, followed by dehydration, decarbonation, and solvent removal methods. Where anhydrous phthalic acid and / or anhydrous maleic acid and / or anhydrous citraconic acid are not sufficiently hydrolyzed, they will remain in the electrolyte 11469pif.doc / 008 17. Residual anhydrous phthalic acid and / or anhydrous maleic acid and / or anhydrous citraconic acid are reacted with ethanol and the like of the reaction solvent to form the esters of the general formulae (4), (5) and (6) ( N). The content of the ester specified in the present invention can be quantified by, for example, nuclear magnetic resonance absorption analysis (NMR). Either (N) can exhibit a characteristic peak of 3 protons at a position of ~ 3.8 PPm when the electrolyte is diluted with heavy DMS and the 1H-NMR analysis is performed at 300 MHz using a nuclear magnetic resonance absorption analyzer. The content of (N) can be quantified by adding a known amount of standard substance to the electrolytic solution and comparing the lH-nmr peak 値 integral ratio of the standard substance with the 1H-NMR peak 値 integral ratio of the above (N). . Examples of the standard substance include chloroform and benzene, and chloroform is preferred. —In order to reduce (N) in electricity, an example can be cited. _) Method and method of lifting __ during the hydrolytic decomposition of anhydrous orthobenzidine = acid, anhydrous maleic acid and anhydrous citric acid. A method for removing residual impurities by crystallization of the fourth __, etc. In the method (1), to which level is the conversion increased, the selection of the reaction conditions such as the molar ratio of water and acid anhydride, temperature, time, etc. is important. When recrystallization is performed in the method (2), the conditions such as the type, house, crystallization temperature, and number of times of the i valley h! I used are important. The methods (1) and (2) may be performed individually or in combination. Examples of the fourth-order ammonium cation (ml) used in the present invention include the species exemplified above as (al). Examples of the electrolyte salt (M) of the present invention include the above-mentioned electrolyte salt (A). 11469pif.doc / 008 18 1220261 Examples of the organic solvent (L) used in the present invention include the above-mentioned organic solvents (B). In addition, the organic solvent (L) may be added with a subsolvent (B ') as described above in the range of 0% by weight to 50% by weight based on the total weight of the electrolytic solution as necessary. As the organic solvent (L), Y-butyrolactone, 3-methyl ~ 2-oxazolidine, and 2-pyrrolidine are preferable. From the viewpoint of electrical conductivity, the content of the electrolyte salt (M) of the electrolytic solution of the present invention is preferably 5% by weight or more, more preferably 10% by weight or more based on the weight of the electrolytic solution. From the viewpoint of solubility, it is preferably 70% by weight or less, and more preferably 40% by weight or less. In the electrolytic solution of the present invention, various additives (P) generally used in the electrolytic solution can be added as necessary. Examples of the additive (P) include the kind described in Example 75 as (D). The total content of (P) is preferably 10% by weight or less based on the total weight of the electrolytic solution. The electrolytic solutions of the first, second, and third inventions of the present invention can be used in electrolytic capacitors. Next, specific embodiments of the present invention will be described, but the present invention is not limited thereto. < Preparation of electrolytic solution > Example 1 Into a 1-liter squeegee, 67.3 g of methanol and 66.2 g of dimethyl carbonate (0.74 mol) were charged and the temperature was raised to 120 ° C under a closed atmosphere. Next, 41.4 g (0.7 mol) of trimethylamine was blown in under 10 hours under pressure to perform a four-stage reaction. The 4-stage conversion of the reaction solution was 92.6%. After that, the temperature was increased to U5 11469pif.doc / 008 19 1220261, while the reaction was tracked by a liquid chromatograph, and the reaction was continued so that the conversion rate of the fourth-stage conversion reached 99.9%, and methanol of tetramethylammonium monomethyl carbonate was obtained. 174.9 g of solution. A 1L 4-neck flask was charged with i08.8 g (0.74 mol) of anhydrous phthalic acid and 189.0 g (10.5 mol) of excess ion-exchanged water, and subjected to a hydrolytic reaction at 95 ° C for 2 hours. . As a result of 1H-NMR analysis, the hydrolytic decomposition rate of anhydrous phthalic acid was 99.9%. Next, 174.9 g of the above-mentioned tetramethylammonium-methyl carbonate was dropped over 4 hours so that the acid / base mol ratio became 1.05. After the dropping was completed, decarbonation, desolvation, and dehydration were performed at 120 ° C, and then reduced pressure to obtain 206 g of tetramethylammonium-phthalate. The commercially available Y-butyrolactone was diluted to have a salt concentration of 25% by weight, and the water content of the electrolytic paper in the capacitor was considered. The water content was adjusted to 5.5% by weight to complete the electrolytic solution. ^ H — As a result of NMR analysis and liquid chromatography analysis, the content of (C1) is 0.01% by weight, the content of (C2) is 0% by weight, and the content of (C3) is 0% by weight, so the hydrolysis of the solvent is decomposed The total content of the substance (C) is 0.01 wt%. The total content of the trimethyl group of the tertiary amine (D) derived from the cations and the trimethylammonium salt of the tertiary ammonium salt (j2) was 0.03% by weight. In addition, the content of (N1) is 0 wt% and the content of (N2) is 0 wt%. The content of (N3) is 0 wt%. Therefore, the total content of the impurity-derived ester (N) derived from the anion is 0 wt%. ° Example 2 Except that 66.2 g (0.74 moles) of dimethyl carbonate was replaced with 86.8 g (0.74 moles) of diethyl carbonate 2 0 11469 pif.doc / 008, and 41. 4 g (4.0 g) of trimethylamine · 7 moles) Substituted with N-methylpyridine 69.4 § (0.7 moles), anhydrous-108.8 g of this monoformic acid (0.74 moles) with 72 maleic anhydride; An electrolytic solution was prepared in the same manner as in Example 1 except for the substitution of 0 g (0.74 mol). In addition, the 4th stage conversion after the 4th stage reaction at 1201: 9 1 _6 / °. -As a result of NMR analysis and liquid chromatography analysis, the content of (C1) is 0.01% by weight, the content of (C2) is 0% by weight, and the content of (C3) is 0% by weight, so the total of (C) The content is 0.01 wt%. The total content of impurities (· Π) and U2) derived from cations was 0.02 wt%. The content of (N1) is 0% by weight, the content of (N2) is 0% by weight, and the content of (N3) is 0% by weight, so the total content of (N) is 0% by weight. Example 3 An electrolytic solution was prepared in the same manner as in Example 1 except that 108.8 g (0.74 mol) of anhydrous phthalic acid was replaced with 82.3 g (0.74 mol) of anhydrous fornic acid. In addition, the 4-stage conversion after the 4-stage reaction at 120 ° C was 91.4%. -The results of NMR analysis and liquid chromatography analysis: '(C1) content is 0.01 wt%, (C2) content is 0 Wt%' (C3) content is Owt%, so the total of (C) The content is 0.01 wt%. In addition, the total amount of impurities (jl) and (j2) derived from cations has a stomach content of 0.02% by weight. The content of (N1) is 0% by weight, the content of (N2) is 0% by weight, and the content of (N3) is 0% by weight, so the total content of (N) is 0% by weight. 11469pif.doc / 008 1220261 Example 4 An electrolytic solution was prepared in the same manner as in Example 1 except that γ-butyrolactone was substituted with 3-methyl-2-oxazolidine. In addition, the 4-stage conversion after the 4-stage reaction at 120 ° C was 91.4%. As a result of iH-NMR analysis and liquid chromatography analysis, the content of (C1) was Owt%, the content of (C2) was 0.01% by weight, and the content of (C3) was Owt%, so the total of (C) The content is O.Olwt%. The total content of impurities (j 1) and (j2) derived from cations was 0.02 wt%. The content of (N1) is 0% by weight, the content of (N2) is 0% by weight, and the content of (N3) is 0% by weight, so the total content of (N) is 0% by weight. Example 5 An electrolytic solution was prepared in the same manner as in Example 1 except that γ-butyrolactone was substituted with 2-pyrrolidine. In addition, the 4th stage conversion after 4th stage reaction at 120 ° C was 91.5%. As a result of -NMR analysis and liquid chromatography analysis, the content of (C1) was Owt%, the content of (C2) was Owt%, and the content of (C3) was 0.02wt%, so the total content of (C) 0.02wt%. The total content of impurities (jl) and (j2) derived from cations was 0.02 wt%. In addition, the content of (N1) is Owt%, the content of (N2) is Owt%, and the content of (N3) is Owt%. Therefore, the total content of (N) is Owt%. Comparative Example 1 Electrolysis was prepared in the same manner as in Example 1 except that the charged amount of anhydrous phthalic acid was 98.4 g (0.67 moles 11469 pif.doc / 008 2 2 1220261 ears) and the acid / base mole ratio was 0.96. liquid. As a result of β-NMR analysis and liquid chromatography analysis, the content of (C1) was 3.1% by weight, the content of (C2) was 0% by weight, and the content of (C3) was 0% by weight, so the total content of (C) The amount was 3.1 wt%. The total content of the impurities (jl) and (j2) from the cations was 0.03% by weight. The content of (N1) is 0% by weight, the content of (N2) is 0% by weight, and the content of (N3) is 0% by weight. Therefore, the total content of (N) is 0% by weight. Comparative Example 2 Electrolysis was performed in the same manner as in Example 1 except that the reheating reaction at 135 ° C was not performed during the quaternary reaction in Example 1 and γ-butyrolactone was replaced with 2-pyrrolidine. liquid. As a result of iH-NMR analysis and liquid chromatography analysis, the content of (C1) was 0.01% by weight, the content of (C2) was 0% by weight, and the content of (C3) was 0% by weight, so (C) The total content is 0.01% by weight. The total content of impurities (jl) and U2) derived from cations was. In addition, since the content of (N1) is 0% by weight, the content of (N2) is 0% by weight, and the content of (N3) is 0% by weight, the total content of (N) is 0% by weight. Comparative Example 3 An electrolytic solution was prepared in the same manner as in Example 2 except that the amount of ion-exchanged water during the hydrolytic reaction of anhydrous citraconic acid in Example 3 was 18.9 g (1.05 mol). As a result of β-NMR analysis and liquid chromatography analysis, the content of (C1) was 0.01% by weight, the content of (C2) was 0% by weight, and the content of (C3) was 11469pif.doc / 008 23 1220261. 〇wt%, so the total content of (C) is 0.01% by weight. The total of f ', the impurities (jl) and (j2) derived from the cations contains * stomach and stomach 0.02 wt%. In addition, the content of (N1) is 0% by weight, the content of (N2) is 0% by weight, and the content of (N3) is 3.2% by weight, so the total content of (N) is 3.2% by weight. Comparative Example 4 An electrolytic solution was prepared in the same manner as in Example 4 except that the charged amount of anhydrous phthalic acid in Example 4 was 98.4 g (0.67 mol) and the acid / base mol ratio was 0.96. As a result of iH-NMR analysis and liquid chromatography analysis, the content of (C1) was Owt%, the content of (C2) was 2.9wt%, and the content of (C3) was Owt%, so the total content of (C) The amount was 2.9 wt%. The total content of the impurities (jl) and (j2) derived from the cations was 0.02 wt%. In addition, since the content of (N1) is 0% by weight, the content of (N2) is 0% by weight, and the content of (N3) is 0% by weight, the total content of (N) is 0% by weight. Comparative Example 5 ° An electrolytic solution was prepared in the same manner as in Example 9 except that the charged amount of anhydrous phthalic acid in Example 5 was 9 (0.67 mol) and the acid / base mol ratio was 0.96. . As a result of U 5 β-NMR analysis and liquid chromatography analysis, (the amount is Owt%, the content of (C2) is 0wt〇 / 〇, and the content of (C3) is 4.0wt%, so (C) And the total content of the impurities (j) and (j2) of the cations is 0j. In addition, the content of (N1) is 0% by weight, and (N2) Contains 0% by weight, 5% by weight, 11469pif.doc / 008 24 1220261 (N3) is 0% by weight, so the total content of (N) is 0% by weight. Examples 1 to 5 and Comparative Examples The contents of impurities in the electrolytic solution described in 1 to 5 are summarized in Table 1. The measurement conditions for 1H-NMR analysis and liquid chromatography analysis are as follows. ≪ NMR analysis > Device: Nuclear magnetic resonance absorption analysis device A- 300 (manufactured by Bruker, Japan) Measurement solvent: Heavy DMSO Frequency: 300 MHz < Liquid chromatograph analysis > Device: High-speed liquid chromatograph LC-10A (manufactured by Shimadzu Corporation) Column: Capcell PAK (manufactured by SHISEIDO) Mobile phase: Ion-exchanged water containing 10 mM phosphate and 100 mM sodium perchlorate. Flow rate: 0.8 ml / min Sample dilution Rate: 100 times dilute with mobile phase_ Sample injection volume: 20μ1 Detector: UVIDEC— 100V Detection wavelength: 210nm Using the electrolytes of Examples 1 to 5 and Comparative Examples 1 to 5 to measure the conductivity, shown in Table 1 The results are as follows: 11469pif.doc / 008 25 [One skimming] Electrical conductivity_ (mS / cm) 11.4 15.7 12.0 10.0 10.0 〇6 σν \ 〇 (N (N 〇 (N) (wt%) ο 〇〇〇〇〇〇〇〇〇 Γν | 〇〇 (Jl) and (J2) (wt%) 0.03 0.02 i_ 0.02 0.02 0.02! 0.03 CX)! 11 M 0.01 0.02 0.02 U (wt%) 0.01 0.01 0.01 0.01 0.02 1 cold 0.01 0.01 On (N 〇 electrolytic Liquid mixing ratio 1 Γ in in in in in in L 丨 CN (N (N < N (N (N (N (N < N < N < N! Solvents γ-butyrotrium γ-butyrolactone γ- Butanyl 3 -methyl-2 -oxazolidine 2 -pyrrolidine γ -butyrolactone 2 -pyrrolidine γ -butyrolactone 3 -methyl-2 -oxazolidine 2 -pyrrolidine electrolyte phthalic acid Monotetramethylammonium maleate mono-N, N-diethylammonium citraconic acid monotetramethylammonium phthalate monotetramethylammonium phthalate monotetramethylammonium phthalate mono Tetramethylammonium Monotetramethylammonium dicarboxylate Monotetramethylammonium phthalate Monotetramethylammonium phthalate Monotetramethylammonium phthalate, 1 / j Example 1 Example 2 Example 3 Example 4 Implementation Example 5 Comparative example 1 Comparative example 2: Comparative example 3 Comparative example 4 j 1 Comparative example 5 9CVJ · OO00POSU 69 inch one 1220261 < Conductivity > The conductivity meter CM-40S manufactured by Toa Radio Co., Ltd. was used. Electrical conductivity at 30 ° C. As can be seen from Table 1, the electrolytic solutions of Examples 1 to 5 of the present invention have superior conductivity characteristics than the electrolytic solutions of Comparative Examples 1 to 5. The electrolytic solution of the present invention has a low content of hydrolysate of a solvent of an impure substance, a tertiary amine, a tertiary ammonium salt, and an ester, and therefore has excellent conductivity. Therefore, by using the electrolytic solution of the present invention, it is possible to improve the performance of the electrolytic capacitor. 11469pif.doc / 008 27